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WO2015029996A1 - Composition de résine de matière de revêtement - Google Patents

Composition de résine de matière de revêtement Download PDF

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Publication number
WO2015029996A1
WO2015029996A1 PCT/JP2014/072295 JP2014072295W WO2015029996A1 WO 2015029996 A1 WO2015029996 A1 WO 2015029996A1 JP 2014072295 W JP2014072295 W JP 2014072295W WO 2015029996 A1 WO2015029996 A1 WO 2015029996A1
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WIPO (PCT)
Prior art keywords
group
component
resin composition
coating material
atom
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PCT/JP2014/072295
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English (en)
Japanese (ja)
Inventor
慶次 後藤
大島　和宏
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電気化学工業株式会社
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Priority to JP2015534231A priority Critical patent/JP6712134B2/ja
Publication of WO2015029996A1 publication Critical patent/WO2015029996A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/12—Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate

Definitions

  • the present invention relates to a resin composition for a coating material used for various sensor elements, display elements and the like, and further to a high refractive index resin composition used for a high refractive index layer of an antireflection film or an optical waveguide film.
  • a coating layer made of an inorganic substance or an organic substance is provided for the purpose of protecting the surface. Furthermore, in recent years, a covering layer in which high refractive index layers and low refractive index layers are alternately stacked is used for the purpose of imparting functions such as antireflection and optical waveguide to the surface protective layer.
  • This high refractive index layer contains a high refractive index inorganic film formed by vapor deposition of ceramics such as titania, zirconia and alumina, and radical polymerizable monomers such as bisphenol A type epoxy (meth) acrylate and urethane (meth) acrylate.
  • the high-refractive-index organic film that is cured by irradiating energy rays such as ultraviolet rays after coating is used according to the purpose, but the former inorganic film is in close contact when the substrate is a film or sheet.
  • photocurable high-refractive-index organic films blended with radically polymerizable monomers have been widely used. It is like that.
  • Patent Documents 1 to 3 disclose a resin composition using sulfur-containing (meth) acrylate. Also known are photocurable resin compositions. Further, for example, Patent Document 4 discloses an active energy ray-curable composition using urethane (meth) acrylate having a diphenyl sulfone structure.
  • 4,4′-dimercaptodiphenyl sulfide dimethacrylate is a bisphenol A type. Although it has a higher refractive index than a compound having an aromatic ring such as epoxy (meth) acrylate, these compounds generally absorb light with a wavelength of 450 nm or less, so they are colored yellow and the transparency tends to decrease. There was a problem that it was difficult to adhere to.
  • Patent Document 5 discloses a compound and a polymer having a dinaphthothiophene skeleton.
  • a photocured film prepared by diluting a photopolymerizable composition using dinaphthothiophene having an ethylenically unsaturated double bond with a solvent such as ethyl acetate is disclosed. (Paragraph number [0143]).
  • the residual solvent due to the influence of the residual solvent, it may cause a decrease in strength and outgassing, and good reliability cannot be obtained, or crystalline components tend to precipitate in the composition when stored for a long time. , The refractive index fluctuates and the coating cannot be performed.
  • the present invention has been made in view of such circumstances, and provides a resin composition for a coating material that has a high refractive index and high transparency and does not require the use of a solvent.
  • a dinaphthothiophene polyene compound having two or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the general formula (1) described later (B) As a component, a polythiol compound, (C) As a component, radical photopolymerization initiator, As the component (D), a polyene compound that is other than dinaphthothiophene and has fewer carbon atoms than the component (A),
  • the content of component (A) is in the range of 5 to 50 parts by mass with respect to the total amount of the composition, and the content of component (B) is 10 to 60 masses with respect to the total amount of the composition.
  • a resin composition for a coating material is provided, wherein the content ratio of the component (D) is in the range of 5 to 85 parts by mass with respect to the total amount of the composition.
  • a polymerization inhibitor is further contained as component (E).
  • the polymerizable functional group of the component (A) is one selected from the group consisting of a vinyl group, a styryl group, a vinyl ether group, an allyl group, an allyl ether group, a (meth) acryloyl group, or a (meth) acrylonitrile group. More than a seed.
  • the polymerizable functional group is an allyl ether group.
  • the component (A) includes 2,12-diallyl ether dinaphthothiophene.
  • the component (D) has 6 to 23 carbon atoms.
  • the component (D) is at least one member selected from the group consisting of (meth) acrylates, allyl compounds, and allyl ether compounds.
  • a covering material comprising the above-described resin composition for a covering material, and a base material (eg, glass, film or sheet) on which the covering material is formed.
  • a base material eg, glass, film or sheet
  • a layer having a refractive index lower than that of the above-mentioned resin composition for a coating material is formed after a layer made of the above-described resin composition for a coating material is formed on a substrate.
  • the resin composition for a coating material of the present invention comprises a resin composition for a coating material containing a dinaphthothiophene-based polyene compound having two or more polymerizable functional groups, a polythiol compound, and a radical polymerization initiator in a specific ratio. Therefore, it has characteristics such as high refractive index and transparency required for surface protection of sensor elements, display elements, antireflection films, optical waveguide films, and the like, and excellent adhesion. Moreover, since the resin composition for coating
  • a coating material is a coating on a substrate such as a glass substrate, a plastic film, or a plastic sheet for the purpose of imparting surface protection, designability, and functionality such as antireflection and optical waveguide. Means the material to be.
  • the “total amount of the resin composition” refers to a total of 100 parts by mass of the component (A), the component (B), and the component (D).
  • the energy ray-curable resin composition according to the present embodiment has, as component (A), dinaphtho having two or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the following general formula (1). It has a thiophene-based polyene compound.
  • each Y is independently a polymerizable functional group represented by the general formula (2), and c is an integer from 2 to 4 provided that c + d is an integer of 2 to 4. And d is an integer of 1 to 3.
  • (R) a or (R) b means a or b identical or different substituents, respectively, which are Each R may be independently bonded to an organic group, hydroxyl group, amino group, nitro group, thiol group, sulfo group, halogen atom, or substituted atom.
  • a is an integer of 0 to 5
  • b is an integer of 0 to 5.
  • each X is independently a single bond, a divalent organic group or a divalent atom
  • each R 1 is independently a hydrogen atom or a methyl group
  • X is 2
  • X represents an alkylene group, an aralkylene group, an alkenylene group, an ester bond, an amide bond, an imide bond or a bond thereof that may contain a hetero atom consisting of an oxygen atom, a sulfur atom or a nitrogen atom.
  • X is a divalent atom
  • X is an oxygen atom, a sulfur atom, a tin atom that may have a bond with another atom, or a phosphorus atom that may have a bond with another atom. is there.
  • X may be bonded to any substitutable carbon atom in the naphthalene ring to which they are bonded.
  • Examples of the polymerizable functional group include a vinyl group, a styryl group, a vinyl ether group, an allyl group, an allyl ether group, a (meth) acryloyl group, a (meth) acrylonitrile group, and the like in terms of transparency and reactivity ( A (meth) acryloyl group or an allyl ether group is preferred, and an allyl ether group is particularly preferred.
  • the dinaphthothiophene compound examples include 2,12-divinyldinaphthothiophene, 3,11-divinyldinaphthothiophene, 5,9-divinyldinaphthothiophene, 2,12-diacryloylmethyldinaphthothiophene, 3,11-Diacryloylmethyldinaphthothiophene, 2,12-dimethacryloylmethyldinaphthothiophene, 3,11-dimethacryloylmethyldinaphthothiophene, 2,12-diallyl ether methyldinaphthothiophene, 3,11-diallyl ether Dinaphthothiophene, 2,12-divinyl ether methyl dinaphthothiophene, 3,11-divinyl ether dinaphthothiophene, 2,12-dimethacryloyloxyethoxydinap
  • the content ratio of the component (A) is preferably 5 to 50 parts by mass with respect to the total amount of the resin composition, and particularly 15 to 45 parts by mass in terms of compatibility between the high refractive index and the component (B). Is more preferable.
  • the content ratio of the component (A) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by mass, and between any two of the numerical values exemplified here. It may be within the range.
  • the dinaphthothiophene-based polyene compound can be produced by the production method exemplified in Patent Documents 5 to 6 or Non-Patent Document 1, but the present invention is not limited to this method, and any product produced by any production method can be used.
  • the resin composition of the present invention contains a polythiol compound as the component (B).
  • the polythiol compound used in the present invention is a substance having an average molecular weight of 50 to 15000 having two or more thiol groups per molecule.
  • polythiol compound used in the present invention examples include mercapto group-substituted alkyl compounds such as dimercaptobutane and trimercaptohexane, mercapto group-substituted allyl compounds such as dimercaptobenzene, trimethylolpropane-tris- ( ⁇ -Thiopropionate), tris-2-hydroxyethyl-isocyanurate tris- ⁇ -mercaptopropionate, pentaerythritol tetrakis ( ⁇ -thiopropionate) and other polyhydric alcohols such as thioglycolic acid and thiopropionic acid Esters, 1,8-dimercapto-3,6-dioxaoctane, 1,11-dimercapto 3,6,9-trioxadodecane, diethylene glycol bisthioglycolate, triethylene glycol bisthioglycolate, tetrae Lenglycol bisthi
  • a reaction product of an alkylene oxide adduct and hydrogen sulfide is preferable, and 1,8-dimercapto-3,6-dioxaoctane is particularly preferable.
  • the content ratio of the component (B) is preferably 10 to 60 parts by mass with respect to the total amount of the resin composition, particularly 20 to 50 parts by mass in terms of high refractive index and compatibility with the component (A). Is more preferable. Specifically, the content ratio of the component (B) is, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 parts by mass, and any of the numerical values exemplified here is 2 It may be within a range between the two.
  • the resin composition of the present embodiment contains (C) a radical photopolymerization initiator.
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals when irradiated with energy rays.
  • photo radical polymerization initiator examples include benzyl derivatives such as benzyl, benzoin, benzoin benzoic acid, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzophenone derivatives such as benzophenone and 4-phenylbenzophenone, and 2,2-diethoxy Alkyl acetophenone derivatives such as acetophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -Phenyl) -2-hydroxy-2-methyl-1-propan-1-one, ⁇ -hydroxyacetophenone derivatives such as 2-hydroxy-2-methyl-1-phenylpropan-1-one Bisdiethylaminobenzophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-
  • alkylacetophenone derivatives ⁇ -hydroxyacetophenones, and phosphine oxides are preferable from the viewpoint of excellent reactivity and transparency, and acylphosphine oxide derivatives are more preferable.
  • acylphosphine oxide derivatives bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferred. These can be used alone or in combination of two or more.
  • the content of component (C) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on the total amount of the resin composition. If it is in the range of 0.1 to 10 parts by mass, the curability will not be deteriorated and the transparency will not be lowered.
  • the content ratio of the component (C) is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by mass, and is exemplified here. It may be within a range between any two of the numerical values.
  • ⁇ (D) component polyene compound other than dinaphthothiophene type>
  • the resin composition of the present invention contains a polyene compound other than dinaphthothiophene as component (D).
  • polyene compounds other than dinaphthothiophene as the component (D) are not limited as long as they are alkenes having two or more carbon-carbon unsaturated bonds per molecule, but include divinylbenzene, divinyltoluene and the like.
  • Vinyl compounds ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri ( (Meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene glycol di (meth) acrylate, and isocyanuric acid ethylene oxide modified tri (meth) acrylate Diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, allyl compounds such as tetraallyloxyethane, allyl ethers such as polyoxypropylene diallyl ether compounds, and the like.
  • divinylbenzene is preferred.
  • isocyanuric acid ethylene oxide-modified tri (meth) acrylate is preferable.
  • allyl compounds triallyl isocyanurate is preferable.
  • a high refractive index is obtained, and the compatibility with (A) component and (B) component and the reactivity are excellent, and among the groups consisting of (meth) acrylates, allyl compounds, and allyl ether compounds. 1 or more types of these are preferable, 1 or more types in the group which consists of an allyl compound and an allyl ether compound are more preferable, and an allyl compound is the most preferable.
  • the number of carbon atoms in the component (D) is less than that of the component (A), for example, 6 to 23, and preferably 6 to 18.
  • the carbon number of the component (D) is, for example, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23. It may be within the range between any two of the numerical values exemplified here. Even if the number of carbon atoms of the component (D) exceeds 23, the component (D) can be used if the number of carbon atoms of the component (D) is less than the number of carbon atoms of the component (A) used in this embodiment.
  • the molecular weight of the component (D) is not particularly limited, but is, for example, 100 to 700, specifically, for example, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, and may be within a range between any two of the numerical values exemplified here.
  • the content ratio of the component (D) is preferably 5 to 85 parts by mass with respect to the total amount of the resin composition, and particularly has a high refractive index, transparency, and compatibility with the components (A) and (B). In this respect, 15 to 65 parts by mass is more preferable.
  • the content ratio of the component (D) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 parts by mass. It may be within the range between any two of the numerical values exemplified here.
  • the resin composition of the present invention includes a monofunctional (meth) acrylate compound, a monofunctional vinyl compound, a monofunctional vinyl ether compound, a monofunctional allyl ether compound, a monofunctional compound, as long as the effects of the invention are not impaired.
  • a thiol compound may be contained.
  • the resin composition of the present invention may contain (E) a polymerization inhibitor for the purpose of imparting storage stability as long as the effects of the invention are not impaired.
  • a polymerization inhibitor 1 or more types in the group which consists of a quinone type compound and a nitrosamine type compound are preferable, and a nitrosamine type compound is more preferable.
  • quinone compounds include ⁇ -naphthoquinone, 2-methoxy-1,4-naphthoquinone, 4-methoxy-1-naphthol, methyl hydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butyl hydroquinone, 2,5-di- Examples thereof include tert-butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone and the like.
  • nitrosamine compound examples include N-nitrosophenylhydroxylamine ammonium salt (cuperon), N-nitrosophenylhydroxylamine aluminum salt, and the like.
  • quinone compounds one or more members selected from the group consisting of hydroquinone and hydroquinone monomethyl ether are preferable.
  • the nitrosamine compounds at least one member selected from the group consisting of cuperone and N-nitrosophenylhydroxylamine aluminum salt is preferable, and N-nitrosophenylhydroxylamine aluminum salt is most preferable.
  • the content of the polymerization inhibitor is preferably 0.00001 to 1.0 parts by mass, more preferably 0.0005 to 0.1 parts by mass, and 0.001 to 0.000 parts by mass with respect to the total amount of the resin composition. Most preferred is 01 parts by weight.
  • the content of the polymerization inhibitor is, for example, 0.00001, 0.0001, 0.0005, 0.001, 0.002, 0.003, 0.004, 0.005, 0. .01, 0.1, and 1 part by mass, and may be within a range between any two of the numerical values exemplified here.
  • ⁇ Other additives As long as the purpose of the present embodiment is not impaired, various elastomers such as antioxidants, silane coupling agents, acrylic rubbers, urethane rubbers, diene rubbers, photosensitizers, light stabilizers, solvents, extenders, fillers Further, additives such as reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants and surfactants may be contained.
  • elastomers such as antioxidants, silane coupling agents, acrylic rubbers, urethane rubbers, diene rubbers, photosensitizers, light stabilizers, solvents, extenders, fillers
  • additives such as reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants and surfactants may be contained.
  • the method for producing the resin composition according to this embodiment is not particularly limited as long as the above materials can be sufficiently mixed.
  • the mixing method of the material is not particularly limited, and examples thereof include a stirring method using a stirring force accompanying rotation of a propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable because stable mixing can be performed at low cost.
  • the resin composition can be cured by irradiation with energy rays using the following light source.
  • the light source used for curing and adhering the resin composition is not particularly limited, but a halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium or the like), a low pressure mercury lamp, a high pressure mercury lamp, Examples include ultra-high pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, and light emitting diodes (hereinafter referred to as LEDs). These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelengths of the respective radical photopolymerization initiators.
  • the above light sources have different emission wavelengths and energy distributions. Therefore, the light source is appropriately selected depending on the reaction wavelength of the radical photopolymerization initiator. Natural light (sunlight) can also be a reaction initiation light source.
  • the light source may perform direct irradiation, focused irradiation with a reflecting mirror or the like, or focused irradiation with a fiber or the like.
  • a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.
  • the resin composition having the above-mentioned structure is quickly cured by irradiation with energy rays, a cured product excellent in optical properties such as high transparency and high refractive index can be provided.
  • the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, and has excellent adhesion to substrates such as glass, plastic film, and plastic sheet. Can be offered as.
  • the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, it can be used as a high refractive index layer of an antireflection film or an optical waveguide film.
  • An optical waveguide film can be provided.
  • the antireflection film and optical waveguide film are coated with a layer made of the resin composition of the present invention (hereinafter referred to as a high refractive index layer) on various substrates such as glass, plastic film, plastic sheet, etc., and irradiated with energy rays. Then, a layer having a lower refractive index than the high refractive index layer (hereinafter referred to as a low refractive index layer) is formed on the high refractive index layer.
  • a layer made of the resin composition of the present invention hereinafter referred to as a high refractive index layer
  • a low refractive index layer a layer having a lower refractive index than the high refractive index layer
  • Base materials include glass base materials such as alkali-free glass, alkali glass, borosilicate glass, and quartz, ceramic base materials such as silica, alumina, and silicon nitride, and metals such as silicone, aluminum, stainless steel, iron, copper, and silver. From resins such as base materials, acrylic resins, styrene resins, carbonate resins, olefin resins, polyester resins, polyimide resins, polyamide resins, epoxy resins, silicone resins, fluorine resins, and cellulose resins A film base material, a sheet base material, and the like can be used.
  • the low refractive index layer examples include inorganic films such as alkali metal fluorides such as magnesium fluoride and potassium fluoride, silica, and the like, and organic films such as fluoropolymers such as polyperfluoroethylene and perfluorocycloolefin.
  • organic films such as fluoropolymers such as polyperfluoroethylene and perfluorocycloolefin.
  • Polyether resins such as polyethylene glycol, silicone resins, acrylic resins, epoxy resins, urethane resins and their fluorine-modified resins can be used.
  • the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, and therefore has a high liquid crystal panel, an organic electroluminescence panel, a touch panel, a projector, a smartphone, a mobile phone, a digital camera, a digital movie display element, It can be used as a coating material used for various sensor parts such as CCD, CMOS, and biochip, semiconductor elements such as flash memory, DRAM, and semiconductor laser, and also as a high refractive index layer of an antireflection film or an optical waveguide film.
  • A Dinaphthothiophene-based polyene compound
  • DAODNT 2,12-diallyl ether dinaphthothiophene
  • B Polythiol compound (B-1) 1,8-dimercapto-3,6-dioxaoctane (“DMDO” manufactured by Maruzen Petrochemical Co., abbreviation: DMDO)
  • B-2) Trimethylolpropane-tris- ( ⁇ -thiopropinate) (“TMMP-20P”, abbreviation: TMMP, manufactured by SC ORGANIC)
  • TMMP-20P Trimethylolpropane-tris- ( ⁇ -thiopropinate)
  • PEMP Pentaerythritol tetrakis (3-mercaptopropionate)
  • PEMP Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate
  • TEMPIC Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate
  • D Polyene compounds other than dinaphthothiophene compounds (D-1) triallyl isocyanurate (carbon number 12, “TAIC” manufactured by Nippon Kasei Co., Ltd., abbreviation: TAIC) (D-2) Isocyanuric acid ethylene oxide-modified triacrylate (18 carbon atoms, “Aronix M-315” manufactured by Toa Gosei Co., Ltd., abbreviation: TAEOC) (D-3) Divinylbenzene (8 carbon atoms, “Divinylbenzene” manufactured by Tokyo Chemical Industry Co., Ltd., abbreviation: DVB) (D-4) Dipentaerythritol hexaacrylate (carbon number 28, “Light acrylate DPE-6A” manufactured by Kyoeisha Chemical Co., Ltd., abbreviation: DPHA, (D-4) is used as a comparative example because it has a large number of carbon atoms)
  • E Polymerization inhibitor (E-1) N-nitrosophenylhydroxylamine aluminum salt (“Q-1301”, abbreviation: NPHAA, manufactured by Wako Pure Chemical Industries, Ltd.)
  • Examples 1 to 13, Comparative Examples 1 to 4 The raw materials of the type shown in Table 1 were mixed at the composition ratio (unit is parts by mass) shown in Table 1, to prepare a resin composition for a coating material, and the evaluation described below was performed. No solvent was used. Various evaluation results are shown in Table 1. Unless otherwise specified, the test was carried out in an environment of 23 ° C. and 50% humidity.
  • a cured product test piece cured under the conditions of an irradiation intensity of 30 mW / cm 2 and an integrated light quantity of 30,000 mJ / cm 2 was prepared, and the refractive index was evaluated.
  • the refractive index was evaluated by measuring the refractive index at a wavelength of 633 nm using a spectroscopic prism coupler refractive index measuring device ("MODEL 2010 PRISM COUPLER" manufactured by Metricon).
  • a cut line was placed in the cured film so as to be 2 mm long ⁇ 2 mm wide ⁇ 25 squares in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then cellophane.
  • a tape (model CT-405AP manufactured by Nichiban Co., Ltd .: width 24 mm, adhesive strength 23 N / 10 mm) was applied and 180 ° peeling was performed. The number of cells remaining after 180 ° peeling was counted and evaluated according to the following criteria. Other conditions that were not specified were in accordance with JIS K 5600-5-6. ⁇ : All 25 sheets remained ⁇ : 15 or more and 24 or less remained x: Less than 14 sheets
  • Comparative Example 1 since the dinaphthothiophene polyene compound was not used, the refractive index and the adhesion of the cured film were not sufficient. In Comparative Example 2, since the blending amount of the dinaphthothiophene polyene compound was too large, in Comparative Example 3, since the polyene compound other than the dinaphthothiophene compound was not blended, the liquid stability was poor and it was not easily redissolved. Since precipitates were generated, a test piece for evaluation could not be prepared. In Comparative Example 4, a polyene compound other than the dinaphthothiophene compound was blended. However, because the polyene compound has too many carbon atoms, a precipitate that does not easily re-dissolve due to poor liquid stability was generated. The test piece could not be made.
  • the resin composition of the present invention is excellent in optical properties such as high transparency and high refractive index, a high liquid crystal panel, organic electroluminescence panel, touch panel, projector, smartphone, mobile phone, digital camera, digital movie display element, Suitable for use as sensor elements for various sensor components such as CCD, CMOS, biochip, coating materials used for semiconductor elements such as flash memory, DRAM, and semiconductor laser, and as a high refractive index layer for antireflection films and optical waveguide films. Can be very useful in industry.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne une composition de résine de matière de revêtement qui a un indice de réfraction élevé et une transparence élevée, et qui ne nécessite pas l'utilisation d'un solvant. Selon la présente invention, on propose une composition de résine de matière de revêtement caractérisée en ce qu'elle contient (1) un constituant (A) composé d'un composé à base de dinaphtothiophène spécifique ayant un ou plusieurs groupes fonctionnels polymérisables ayant une double liaison éthyléniquement insaturée, un constituant (B) composé d'un composé polythiol, un constituant (C) composé d'un initiateur de polymérisation photo-radicalaire, et un constituant (D) composé d'un composé polyène qui n'est pas à base de dinaphtothiophène et qui a un nombre de carbone inférieur au constituant (A), le constituant (A) étant contenu dans une proportion dans une plage de 5-50 parties en masse par rapport à la quantité totale de la composition, le constituant (B) étant contenu dans une proportion dans une plage de 10-60 parties en masse par rapport à la quantité totale de la composition et le constituant (D) étant contenu dans une proportion dans une plage de 5-85 parties en masse par rapport à la quantité totale de la composition.
PCT/JP2014/072295 2013-08-30 2014-08-26 Composition de résine de matière de revêtement WO2015029996A1 (fr)

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JP2015048368A (ja) * 2013-08-30 2015-03-16 電気化学工業株式会社 光学部品用高屈折率接着剤組成物
WO2016181422A1 (fr) * 2015-05-11 2016-11-17 日立化成株式会社 Film de réglage d'indice de réfraction photosensible du type à transfert, procédé de formation de modèle d'indice de réfraction et composant électronique
US11427656B2 (en) * 2016-08-30 2022-08-30 Sony Corporation Photosensitive composition for hologram recording, hologram recording medium, and hologram

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JP6712134B2 (ja) * 2013-08-30 2020-06-17 デンカ株式会社 被覆材用樹脂組成物
JP6901815B1 (ja) * 2021-04-02 2021-07-14 株式会社石川エナジーリサーチ 飛行装置

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WO2016181422A1 (fr) * 2015-05-11 2016-11-17 日立化成株式会社 Film de réglage d'indice de réfraction photosensible du type à transfert, procédé de formation de modèle d'indice de réfraction et composant électronique
US11427656B2 (en) * 2016-08-30 2022-08-30 Sony Corporation Photosensitive composition for hologram recording, hologram recording medium, and hologram

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